Boron fluoride recovery process



Jne 26, 1945. w. N. AXE

BORON FLUORIDE RECOVERY PROCESS' Filed Dec. 5, 1942 Haddluis aaauosav ll'lL INVENTOR. WILLIAM N. AX E ZEMJO i Lv BY /M A TTORNEYS @Patenten im@ ae, ieee Para v arrests. y l

- noaon rLUomnn nanowar rnoouss o William N. Axe,i Bartlesville, Okla., assigner Yto Phillips ll'etroleum Company, a corporation of Delac separation December 5, .1942, serial No. 468,017

i3 Glaims. This invention relates .to an improvedmethod for the concentration and recovery of boron hal f ides. In one modification this invention relates to the recovery of boron uoride from hydrocarbons and mixtures of hydrocarbon'and inert gases. In a morespeci'c modification this in-` vention relates to an improved process Afor the absorption of boron iiuoride from a hydrocarbon gas stream followed by subsequent recovery of substantially pure boronuoride from the'absorbent. y

Recently it has been discovered that boron fluoride and coordination compounds o boron :liucxide possess unusual catalytic activity when applied to a wide variety of polymerization, isomerization and alkylation reactions. Industrial dedevelopment oi `the catalytic potentialities of boron uoride has been slow, both because of the high initial catalyst cost and because of the loss of gaseous boron fluoride encountered in said reactions. AEven more recently it has been discovered that exceptional catalyst life in alkyla- Vtion andv other reactions can be realized by the continuous activation of boron fluoride complex compounds vwith gaseous boron fluoride. such processes embody novel and improved methods for eration, for the. ultimate regeneration of the n 'boron fluoride.

An object of my invention is to recover boron A fluoride.

5 Itis also an object of the present invention to eiect efficient and economical recovery of boron iluoride from hydrocarbon streams.

Another object of this `invention is to provde a process whereby boron fluoride can be continuously4 recovered from euent streams ofhydro- A further object of the invention is to providev carbons from reactions of the type described and returned to the reaction zone without appreciablel loss of boron fluoride or consumption` of chemicals. A

new compositions of matter.

These and other objects will be apparent from Athe accompanying disclosure and discussion.

I have discovered thatcertain organic sulfurcontaining compounds are capablc'of forming coordination compounds with boron iluoride at substantially atmospheric temperature to form' combinations containing approximately one mol of BF; per mol of absorbent. I have also discovered that thecomplex compounds formed beproducing valuable materials such as high octane blending agents for aviation fuel.

'I'he chemical activity of borcnfluoride is well' known and its removal from gaseous .or liquidhydrocarbon streams by means of aqueous alkaline solutions and the like is ordinarily a relatively .simple operation. However, the recovery of boron uoride from the resultant compounds and solutions, represents a serious problem. lt has been proposed, for example, to employ ammonia and amines as agents for the recovery of boron fluo- Iride.l However, the ammonia-boron fluoride re' action product is` anV exceedingly stable compound requiring the employment of 100 per cent tween boron fluoride and the aforesaid organic sulfur compounds decompose at moderately elevatd temperatures to afford substantially .complete recovery of the constituent compounds.

The' organic sulfur-containing compounds of this invention may be selected from a group corresponding to the following type formula:

l where R' lmay be eitherl an alkyl or aryl radical with or without substituents other than hydrogen and R" may be hydrogen or an alkyl radical with or without substituents other than hy-V drogen. The compound.V or compounds, used should eltherbe' liquid at the absorption temsulfuric acid and temperatures of about 410 F'.

i for liberation of the boron fluoride. The' disad perature or soluble in substantial amounts in suitable liquid material, such as a hydrocarbon fraction. Generally it will be satisfactory to use a compound `in which neitherR nor R contains more than about seven carbon atoms.

A mol of sulfide or mercaptan. The boron fluoride Alkyl sulfldes and mercaptans combine with boron uoride at moderate temperatures of from about 40 to 100 Frto form loose laddition compounds containing one mol of boron fluoride per addition comounds with the aforementioned sulides and mercaptans can be decomposed b y the simple application of heat.- Ordinarily complete decomposition into the constituent compounds is realized at temperatures of about 150 to about vention is particularly adaptable to alkylation' processes., Thus, in cases where boron uoride vcomplex compounds .are employed as catalysts, the leflluent hydrocarbon stream'from the reactor may contain from about 0.5 to 2.0 or more per cent by weight of free. boron fluoride depending on the catalyst composition and the .reaction conditions.. In actualplant operation appreciable quantities of methane, ethane and propane may be present in the feed stocks and therefore wi ll have to be removed from the reactor eluent. Since boron uoride boils intermediate between methane and thane, the pressure stabilizer may be so operated that fixed gases, methane, ethane, propane and boron fluoride are removed in one operation leaving the C4 and higher hydrocarbons substantially free of boron fluoride. The overhead light gases may then be contacted in a suitable countercurrent operation with a selectedalkyl sulfideror mercaptan to absorb the boron fluoride from the gas stream.

A Boron fluoride is subsequently removed from the absorbing liquidin a stripping column operated at a temperature level suiicient to effect decomposition ofthe boron fluoride complex at a satisfactory rate.- 'Ihe gaseous boron fluoride is then compressed and returned to the alkylation system.

A` specific embodiment of the process is illustrated inthe -flow diagram which shows an arrangement of equipment for the continuous recovery of boron fluoride in connection with an alkylation process. A selected isoparain feed mixed with boron fluoride is introduced into the reaction vessel d through line l. Simultaneous ly, an' olefin-containing hydrocarbon fraction is fed to the reactor through line 2 in controlled molar proportions, and the hydrocarbon reactants are' contacted in reactor t with a catalyst containing boron uoride. The eiiluent hydrocarbon mixture 'from' the reactor, containing minor quantities ,of propane and lighter hydrocarbons usually, associated with the feed stocks and boron fluoride dissolved in alkylate and excess isoparaflin, is'fed into a fractionating column through line v5. vThe C3 and lighter hydrocarbons and boron fluoride are removed as gases through line t while `the C4 and heavier hydrocarbons constipounds readily combine with one molecular proportion of boron fluoride. Boron iluoride is substantially completely regenerated from such com'- plex compounds at or below the boiling temperature of the pure absorbent. In 'the caseof the higher sulfldes andmercaptans complete decomfidesy and/or mercaptans maybe satisfactorily employed. liurtherrnore, mixtures of suldes and mercaptans are operable. While the absorbente may contain relatively inert impurities or diluents' it is preferred to employ compounds or mixtures relatively free of alcoholic impurities. Thus, methyl and ethylalcohols form relatively heat-stable complex compounds with boron fluoride While the higher alcohols tend to formhighmolecular weight polymers.

In actualvoperation of this process, complete stoichiometric saturation of the sulde and/or .mercaptan absorbents`is not necessary and in many'instances may be undesirable. Where the concentration of BFa in the gas stream is about 10 weight per cent or less, incomplete saturation of the absorbent may be desirable'in order to favor complete absorption of 'theboron fluoride.

Absorber' pressures are chosen in accordance with the composition'of the ygas s For streams rich in Cs hydrocarbons the pressure may vary from atmospheric .to about 100 pounds gage, while for streams rich in methane and ethane pressures as'high as 500 pounds 'gage may be employed. In order to prevent excessive ac cumulation of hydrocarbons in the-sulde or mercaptan, gas-liquidl contacting is preferred' and pressures are necessarily regulated to maintain this condition. in the stripping zone, low supervatmospheric pressures are ordinarily employed which enable the desorption of boron iluoride at moderate temperatures without, however, incur-A ring losses of the absorbing liquid. In come cas,

tuting lthe kettle product are removed' through line 'l for further stabilization. The boron luoride-containing gases'are fed into the bottom of absorber` t and the boron uorlde is removedby gaseous boron fluoride until completely saturated suicient heat is appliedto decompose the complex. Hot alkyl sulfide is removed through line i3 and through a cooler (not shown) to storage tank It, A partial condenser l@ is employed to prevent the loss of absorbent in the BFa taken overhead through line i6. The low-pressure boron fluoride is compressed to the reactor Workl sub-atmospheric pressures may be feasible. l

- The following exemplary operations will serve to illustrate specific procedures in g out the process of this invention. The examples are not; however, necessarily to be construed as limitations on the practice of the invention.

Example! The following compounds were treated with at a temperature rof F.:

Mols Compound BFz/mol of cpd.

Ethyl 4sulfide` y n-Propyl sulfide Iso-propyl sulde. n-Butyl sulfide n-Amyl sulfide. Methyl disulilde.

The reaction products obtained from boron fluoride and the preceding sulfur compounds -were fuming mobile liquids at atmospheric temperature and pressure. Complete decomposition with substantially complete boron fluoride recov- Example I I A gas stream containing 90 per cent ethane an per cent boron uoride was separated from the effluent of an isobutane-ethylene alkylationreaction carried out in the presence of a catalyst activated with boron fluoride. rI'his gas mixture was introduced at atmospheric pressure into the bottom of a packed column countercurrent to a descending stream of n-butyl sulfide. Complete absorption of boron fluoride was obtained. The liquid taken from the column showed the n-butyl sulfide to be about 50 per cent saturated withvrespect to boron uoride. Desorption of the boron uoride-rich absorbent resulted in more than 95 per cent recovery of substantially pure boron uoride when the absorbent was heated to 205a F.

t will be readily appreciated that various modifications of my invention may be practiced, in the light of the disclosure, without departing from the spirit of the disclosure or from the scope of the claims.

l claim: l. i process for recovering boron fluoride in concentrated form from a gaseous mixture containing 'boron 'fluoride and substantial amounts of other components, which comprises passing such a mixture into Contact with a liquid comprising a sulfur compound of the type R-S-R" where it is ,one of the group consisting of alkyl and aryl radicals and R" is one of the groupiconsisting of hydrogen and alkyl radicals, whereby a complex of said compound and boron fluoride is `formed, removing the resulting rich liquidl absorbent yto a stripping zone, heating said liquid in said stripping zone to a temperature suflloient to decompose said complex forming boron fluoride, and recovering boron fluoride from Vsaid stripping zone.

2. A process for recovering boron iiuoride from a mixture containing boron uoride and substantial amounts of other components substantially yinert under the conditions of use, which comprises passing such a mixture into contact with an organic sulfur compound of the type R'S-R" Where R is one of the group consisting of alkyl and aryl radicals and R'"v is one o f the group consisting of hydrogen and alkyl radicals, under conditions effecting formation of a complex of said compound and boron fluoride, separating said complex from said other components, and heating said complex to a temperaa ture sucient to decompose same thus forming boron fluoride.

3. A process which comprises passing a gaseous mixture containing boron uoride and other gases substantially inert under the conditionsv of use into contact witha liquid comprising an organic sulfurcompound of the type R'SR" where R' is one of the group consisting of alkyl and aryl radicals and Rf is one ofthe group consisting of hydrogen and alkyl radicals, at a tempera--l ture below the decomposition temperature oi the resultant boron fluoride-forganicl sulfur compound complex, for such a time and in such quantities as to effect substantially complete reaction of compound of the type R'-S-R." where R' is one lof thegroup consisting of alkyl and aryl radicals and R," is 4one of the group consisting of hydrogen andalkyl radicals, to a temperature suicient to decompose said complex and form boron uoride and said organic sulfur compound.

5. A process which comprises reacting boron fluoride with an organic sulfur compound of the type R'ns-R" where R' is one of the group consistingA of alkyl and aryl radicals and. R" is one of the group consisting of hydrogen and alkyl radicals, Ain equimolecular proportions at a temperature below the decomposition temperature of the resultant compound, and recovering the re sultant compound which is a mobile fuming liquid at atmospheric temperatures and pressures and is readily decomposable by heat tol produce free boron fluoride and free organic sulfur compound.

6. A process which comprises :reacting boron fluoride with a butyl sulfide in equimoleoular proportions at a temperature below the decomposi tion temperature of the resultant compound, to form a liquid complex readily decomposable at a temperature within therange of about 150 to about 250 F.

"1. A process which comprises reacting boro position temperature of the resultant compound.

to form a liquid complex readily decomposable at a temperature within the range of about 15G to about 250 F,

9. A composition of matter comprising an essentially pure complex resulting from reacting boron uorlde with an equimolar quantity or an organic sulfur compound of the type TRI-S- where R is one of the group consisting of alkyl and aryl radicals and R".is one of the group con- 4 sisting oi hydrogen and alkyl radicals, said complex being a mobile turning liquid at atmospheric temperatures and pressures, and readily decomposable by heat to produce free boron iiuoride and free organic sulfur compound above-described.`

10. A composition of matter as defined in claim 9 in which each said alkyl and aryl radical colltains not more than seven carbon atoms..

V11. A composition of matter comprising the complex resulting from reacting boron fluoride with an equimolar quantity of a butyl mei-captan, said complex being a mobile fuming liquid at atmospheric temperatures and pressures, and readily. decomposable at a temperature within the range of about to about 250 F. to produce free boron uoride and free butyl mercaptan.

12. A composition of matter comprising the complex resulting from reacting' boron fluoride with an equimolar quantity of a butyl sulilde, said sampler: kseng a mobile ing red liquid at atmync tempera@ and meures, and readil? Kecompufsabe at e, temperature within' the mage ef. sham: 150 to about 250 F. to produce im@ basan -uorde and free butyl sulde.

E3. A -mpsion of matter comprising the Q-@mpx esutimg from reacting boron uoride Y L .gspeas I with an muimolm quantity f am amm sulde,y

said wmpez being a mom@ ing liquid gia-atmospheric temperatures' and, pressures, and reily decomposable at 'a temperatm'e within the .range of about 150 to about 250 F. t@ pxoduce free boron uoride and `free amy sude. 

